EP1737896A1 - Novel hydrogels based on polyvinyl alcohols and polyvinyl alcohol copolymers - Google Patents

Novel hydrogels based on polyvinyl alcohols and polyvinyl alcohol copolymers

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Publication number
EP1737896A1
EP1737896A1 EP05744213A EP05744213A EP1737896A1 EP 1737896 A1 EP1737896 A1 EP 1737896A1 EP 05744213 A EP05744213 A EP 05744213A EP 05744213 A EP05744213 A EP 05744213A EP 1737896 A1 EP1737896 A1 EP 1737896A1
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Prior art keywords
group
polyvinyl alcohol
polyvinyl
different
integer
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EP05744213A
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German (de)
French (fr)
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EP1737896B1 (en
Inventor
Jörg SCHULTE
Tim Dickner
Monika Bruckmann
Jörg SCHOTTEK
Uwe Blank
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Celanese Ventures GmbH
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Celanese Ventures GmbH
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F16/04—Acyclic compounds
    • C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to hydrogels containing polyvinyl alcohols and / or
  • Polyvinyl alcohol copolymers processes for the preparation of the hydrogels, and the use of the hydrogels as materials in the biomedical and pharmaceutical fields, for the production of contact lenses, for the controlled release of active substances, as a carrier material for inclusion - immobilized biocatalysts, as a carrier material for transition metal catalysts, as a material for the production of reactive membranes, as an additive to drilling fluids, as a displacer in oil production, as an additive for cement and as an additive to highly viscous liquids, such as Petroleum to improve the flow behavior and for faster transport, as well as a component of cosmetic articles.
  • Hydrogels are water-containing gels based on hydrophilic polymers that exist as three-dimensional networks. As hydrogels, these polymers are insoluble in water, but swell up to an equilibrium volume while largely maintaining their shape. Networking takes place primarily via chemical linking of the individual polymer chains, but is also physically possible through electrostatic, hydrophobic or dipole / dipole interactions between individual segments of the polymer chains.
  • the desired properties of the hydrogels can be set in a targeted manner via the choice of the monomers used for the polymer structure, the type of crosslinking and the crosslinking density.
  • the necessary hydrophilicity of the polymers provides, among other things,
  • Synthetic hydrogels are based on on poly (meth) acrylic acids, poly (meth) acrylicates, polyvinylpyrrolidone or polyvinyl alcohol. Hydrogels are generally well compatible with living tissues (source: Römpp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999).
  • Hydrogels based on polyvinyl alcohol are known (cf. US2003008396A1, US2001029399A1, US0006231605B1, US0005981826A, WO2001044307A3, W01998050017A1, Hassan, Christie M .; Peppas, Nikolaos, A .; Advances in Polymer Science. (2000, 153, 153), Polymer Hydrogel Anionic Polymerization
  • Hydrogels based on polyvinyl alcohol can be produced by various methods, such as, for example, by repeated freezing and.
  • ionizing radiation UV light, gamma radiation
  • cross-linking reagents such as glutaraldehyde, acetaldehyde, formaldehyde, maleic acid, oxalic acid, alginic acid, dimethyl urea, glyoxal, hydrochloric acid, polyacrolein , Diisocyanates and / or divinyl sulfate.
  • Hydrogels based on polyvinyl alcohol are usually made from conventional, linear polyvinyl alcohol. This causes the hydrogel to become cloudy due to crystalline areas, which means that the hydrogels made from conventional polyvinyl alcohol are only suitable for optical applications, such as contact lenses, to a limited extent. Furthermore, hydrogels made from conventional polyvinyl alcohol only acquire their mechanical properties when they are crosslinked to form the hydrogel.
  • hydrogels made of polyvinyl alcohols with special geometries such as, for example, star-shaped geometries, as described in DE10343607 (Schulte et al. / Celanese Ventures GmbH) and DE10356574 (Bruckmann et al. / Celanese Ventures GmbH), have a lower degree of microcrystallinity in the hydrogel, which leads to improved optical properties and improved mechanical properties.
  • the special geometry of the polyvinyl alcohols leads to reduced abrasion by crosslinking the polymers before the hydrogel is formed.
  • the present invention thus relates to hydrogels containing at least one polyvinyl alcohol stamp polymer.
  • hydrogels containing at least one polyvinyl alcohol stem polymer are understood to mean both hydrogels in which one or more polyvinyl alcohol star polymers are used exclusively as a polymer, and also mixtures between polyvinyl alcohol star polymers with other polymers.
  • Mixtures of polyvinyl alcohol stamp polymers with conventional polyvinyl alcohol in a ratio of 99: 1 to 1:99 are particularly preferred.
  • Mixtures of polyvinyl alcohol stamp polymers with polyacrylic acids, polymethacrylic acids, polyacrylates, polymethacrylates and polyvinylpyrrolidone in a ratio of 99: 1 to are also particularly preferred
  • the hydrogels according to the invention contain, in addition to the above-mentioned polyvinyl alcohol stamp polymers, as the name already shows, water.
  • Polyvinyl alcohols with special geometries can be produced by different methods, on the one hand via a transition metal-catalyzed production of polyvinyl acetate as described in DE10238659, followed by saponification as described in DE10343607 or via a copolymerization of vinyl acetate with crosslinking comonomers, followed by saponification as described in DE10356574.
  • polyvinyl alcohols and polyvinyl alcohol copolymers described in DE10343607 and DE10356574 are described as polyvinyl alcohol.
  • Polyvinyl alcohol stamped polymers according to DE10343607 and DE10356574 include compounds of the formula I, II and III
  • Pol stands for a polymer based on a polyvinyl alcohol, particularly preferably for a homo- or copolymer based on polyvinyl alcohol, very particularly preferably polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymer, polyvinyl alcohol-polyethylene copolymer, polyvinyl alcohol-polyvinyl chloride copolymer and Polyvinyl alcohol-polyacrylic acid methyl ester copolymer, and denotes a central atom and is an atom from the 13th to 16th group of the Periodic Table of the Elements, preferably carbon, silicon, nitrogen, phosphorus, oxygen or sulfur, particularly preferably carbon or silicon, and
  • X 1 is in each case the same or different, and is a halogen atom, preferably fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine, and
  • R 1 is the same or different and is hydrogen or a Ci - C 20 carbon-containing group
  • R ⁇ is the same or different and is a bridging Ci - C 20 carbon-containing group between the central atom Z and the initiating unit [R 3 -X 1 ] or silicon or oxygen, and R 3 is the same or different and means carbon or silicon, and
  • R 4 is the same or different and is a hydrogen atom or a Ci - C 20 carbon-containing group
  • R 5 is identical or different and denotes hydrogen or a Ci - C 20 carbon-containing group
  • I is a whole natural number and stands for zero, 1, 2 or 3, and m is in each case identical or different and is a whole natural number and stands for zero, 1, 2, 3, 4 and 5, and n each is equal to or is different and is an integer and for zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 and 20 is and o is the same or different and is 1 or 2, and p is the same or different and is an integer and is 1, 2, 3, 4 and 5, and q is an integer and stands for 2, 3 and 4, and
  • Ar is an aromatic backbone with at least four carbon atoms, in which one or more carbon atoms can be replaced by boron, nitrogen or phosphorus, and preferred aromatic or heteroaromatic backbones are derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, quinoline , Pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, which may also be substituted, which may also be substituted and y is an integer and is zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 and
  • Ap is a cyclic non-aromatic backbone with at least three carbon atoms, which can also contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, preferred aliphatic backbones from the group cycloalkyl, such as, for example, cyciopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, Cyclooctyl, Cyclononyl, or from the group cycloheteroalkyl, such as, for example, aziridine, azetidine, pyrrolidine, piperidine, azepane, azocane, 1, 3,5-triazinane, 1, 3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran , Pyran, Dihydropyran, ' Tetrahydropyran, Oxepan, Oxocan, or from the group of saccharides
  • Polyvinyl alcohol copolymers based on polyvinyl ester copolymers are by a method comprising the steps of: A) radical solution or bulk polymerization of vinyl esters in the presence of a radical generator and, if appropriate, in the presence of a radical scavenger, B) addition of a polyalkenyl compound capable of crosslinking , C) optionally working up and isolation of the polyvinyl ester copolymers formed, D) saponification of the polyvinyl ester / polyvinyl ester-polyalkene mixture produced in B) or of the polyvinyl ester-polyalkene copolymers isolated under C) with the formation of the polyvinyl alcohol-polyvinyl alcohol-polyalkene mixtures or Polyvinyl alcohol-polyalkene copolymers and insulation of the products,
  • R 6 is a C ⁇ - C 2 o aryl group, a C5 - C 2 o heteroaryl group, a C 4 -C 2 o cycloalkyl group, a C -C 20 heterocycloalkyl group or a C 1 - C 20 alkyl group means in which one or more non-directly adjacent C atoms can be replaced by an element of the 5th or 6th group of elements, preferably nitrogen, phosphorus, oxygen or sulfur, particularly preferably nitrogen or oxygen, and
  • R 7 is the same or different and is hydrogen, oxygen, sulfur or a hydroxy group, a carbamoyl group, an amino group, one Carboxy group, a Ci - C 20 alkylcarbonyl group, a Ci - C 20 alkyloxy group, a C 6 - C 20 aryloxy group, an imino group, a Ci - C 2 o alkylimino group, a C 6 - C 20 alkylimino group, a cyano group , a Ci - C 2 o - alkyl group, a C ⁇ - C 2 o aryl group, a C 5 - C 2 o - heteroaryl group, a C 4 -C 20 cycloalkyl group, a C 4 -C 2 o heterocycloalkyl a C 7 - C 2 o -alkylaryl group, a C 7 - C 3 o-arylalkyl group, a C 2 - C- 2 O-
  • residues CC 2 o-alkyl, particularly preferably methyl, are preferably selected from a group containing C 1 -C 2 o-carbon,
  • Ci - C 20 - alkenyl particularly preferably ethenyl, propenyi, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, octenyl or cyclooctenyl
  • Ci - C 2 o - alkynyl particularly preferably ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl, C6 - C 2 o-aryl, particularly
  • C 7 -C 2 o-alkylaryl particularly preferably benzyl, ethylphenyl, propylphenyl, diphenylmethyl, triphenylmethyl or naphthalinylmethyl
  • C 7 -C 2o-aryloxyalkyl particularly preferably o-methoxyphenyl, m-phenoxymethyl, p-phenoxymethyl, C 12 - C2o-aryloxyaryl , particularly preferably p-phenoxyphenyl, C 5 -C 2 o-heteroaryl, particularly preferably 2-pyridyl, 3-pyridyl, 4-pyridyl, quinolinyl, isoquinolinyl,
  • a bridging C 1 -C 2 -carbon-containing group is preferably C 1 -C 2 -alkyl, particularly preferably methylene, ethylene, propylene, butylene, pentylene, cyclopentylene, hexylene or cyclohexylene, d- C 2 o- Alkenyl, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl or cyclohexenyl, C 1 -C 2 -alkynyl, particularly preferred
  • Another object of the present invention is the production and use of the hydrogels according to the invention.
  • hydrogels according to the invention containing a polyvinyl alcohol star polymer can be prepared, for example, by:
  • Reaction in aqueous solution containing a polyvinyl alcohol stamping polymer and optionally further components with cross-linking reagents such as glutaraldehyde, acetaldehyde, formaldehyde, maleic acid, oxalic acid, alginic acid, dimethyl urea, glyoxal, hydrochloric acid, polyacrolein, diisocyanates and / or divinyl sulfate, optionally under acid or Base catalysis.
  • cross-linking reagents such as glutaraldehyde, acetaldehyde, formaldehyde, maleic acid, oxalic acid, alginic acid, dimethyl urea, glyoxal, hydrochloric acid, polyacrolein, diisocyanates and / or divinyl sulfate, optionally under acid or Base catalysis.
  • cross-linking reagents such as glutaraldehyde,
  • polymers such as, for example, polyacrylic acids, polymethacrylic acids, polyacrylates, polymethacrylates and polyvinylpyrrolidone,
  • Alginic acid derivatives such as sodium alginate
  • Salts such as sodium carbonate, potassium carbonate, calcium carbonate, ammonium carbonate, magnesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydrogen carbonate, sodium sulfate, potassium sulfate, ammonium sulfate, magnesium sulfate, sodium phosphate, potassium phosphate, ammonium phosphate, magnesium phosphate, sodium chloride, potassium chloride, ammonium chloride and calcium chloride, calcium chloride, calcium chloride or understood aluminum chloride.
  • hydrogels according to the invention are distinguished from hydrogels from conventional polymers by a higher degree of clarity (comparison of the haze values: see examples 3 and 4).
  • hydrogels according to the invention are distinguished from hydrogels from conventional polymers by a higher resistance to water, which is advantageous when used as a carrier material for inclusion-immobilized biocatalysts, for example for wastewater treatment (comparison of resistance to water: see examples 7 and 8 ).
  • hydrogels according to the invention are products made from mixtures of:
  • Polyvinyl alcohol star polymer (s) and water are Polyvinyl alcohol star polymer (s) and water,
  • Polyvinyl alcohol star polymer (s), conventional polyvinyl alcohol and water,
  • Polyvinyl alcohol stamp polymer (s), conventional polyvinyl alcohol, sodium alginate, calcium chloride, formaldehyde and water,
  • Polyvinyl alcohol star polymer (s), conventional polyvinyl alcohol, microorganisms and water,
  • polyvinyl alcohol star polymer (s) as: • Materials in the biomedical and pharmaceutical fields, for example as artificial tissue or for wound treatment as material for the production of contact lenses as material for the controlled release of active substances as Carrier material for inclusion - immobilized biocatalysts, for example for wastewater treatment as a carrier material for transition metal catalysts, for example palladium catalysts as material for the production of reactive membranes, as an additive to drilling fluids, in particular, due to the degradability, as an additive to drilling fluids for offshore applications as a displacement agent Oil production as an additive for cement as an additive to highly viscous liquids such as petroleum to improve the flow behavior and for faster transport as a component of cosmetic products Pedal.
  • Materials in the biomedical and pharmaceutical fields for example as artificial tissue or for wound treatment as material for the production of contact lenses as material for the controlled release of active substances as Carrier material for inclusion - immobilized biocatalysts, for example for wastewater treatment as a carrier material for transition metal catalysts, for example palladium catalysts
  • Example 1 Preparation of a polyvinyl alcohol stem polymer according to DE10343607
  • the volatile constituents are removed in an oil pump vacuum and the polyvinyl acetate star polymer is taken up in 200 ml of methanol ml of a 1% NaOH solution in methanol is added dropwise, and the mixture is stirred for a further 90 minutes at 50 ° C.
  • the polyvinyl alcohol is filtered off, washed neutral with methanol and dried in an oil pump vacuum.
  • Example 3 Preparation of a hydrogel containing a polyvinyl alcohol stamp polymer
  • polyvinyl alcohol stamp polymer (Example 1) are dissolved at 70 ° C. in 75 ml of demineralized water. The solution is placed in a flat metal bowl (20 x 20 cm), covered with a lid and stored for 12 hours at -30 ° C. The solution is then allowed to come to room temperature within 12 h and the freeze-thaw process is repeated twice. The hydrogel is obtained in the form of a 0.25 cm thick film. Turbidity (Haze value in percent): 1.3.
  • Example 4 Preparation of a hydrogel containing a linear polyvinyl alcohol (comparative example)
  • Example 5 Preparation of a hydrogel containing a mixture of a polyvinyl alcohol star polymer with a linear polyvinyl alcohol
  • the particles are isolated by careful filtration through a glass frit and added to a 40 ° C solution of 5 g formaldehyde (37% in water), 50 g concentrated sulfuric acid and 25 g sodium sulfate. After one hour, the solidified spherical particles are isolated by filtration and washed neutral with water. Yield: 43 g of hydrogel as spherical particles.
  • Example 6 Preparation of a hydrogel containing a linear polyvinyl alcohol (comparative example)
  • Example 7 Investigation of the wear of the hydrogel from Example 5
  • hydrogel from Example 5 In a 50 ml disposable syringe, on the bottom of which there is a plastic sieve (mesh size 0.75 mm), 10 g of hydrogel from Example 5 were added. The hydrogel was covered with a plastic sieve and the cavity above the hydrogel with
  • Example 8 Examination of the wear of the hydrogel from example 6 (comparative example) In a 50 ml disposable syringe, on the bottom of which a plastic sieve (mesh size

Abstract

The invention relates to hydrogels containing polyvinyl alcohols and/or polyvinyl alcohol copolymers having special geometries, methods for the production of said hydrogels, and the use of the hydrogels as materials in the biomedical and pharmaceutical field, for producing contact lenses, for the controlled release of active substances, as a carrier material for inclusion-immobilized biocatalysts, a carrier material for transition metal catalysts, a material for producing reactive membranes, an additive to drilling fluid, a displacing agent in oil recovery, a cement additive and an additive to highly viscous liquids such as crude oil to improve the flowability and increase the speed of conveyance, and a component of cosmetic products.

Description

Beschreibung NEUE HYDROGELE AUF BASIS VON POLYVINYLALKOHOLEN UND POLYVINYLALKOHOL-COPOLYMERENDescription NEW HYDROGELS BASED ON POLYVINYL ALCOHOLS AND POLYVINYL ALCOHOL COPOLYMERS
Die vorliegende Erfindung betrifft Hydrogele enthaltend Polyvinylalkohole und/oderThe present invention relates to hydrogels containing polyvinyl alcohols and / or
Polyvinylalkohol-Copolymere, Verfahren zur Herstellung der Hydrogele, und die Verwendung der Hydrogele als Materialien im biomedizinischen und pharmazeutischen Bereich, zur Herstellung von Kontaktlinsen, zur kontrollierten Freisetzung von Wirkstoffen, als Trägermaterial für Einschluß - immobilisierte Biokatalysatoren, als Trägermaterial für Übergangsmetallkatalysatoren, als Material für die Herstellung von Reaktivmembranen, als Zusatz zu Bohrflüssigkeiten, als Verdrängungsmittel bei der Ölförderung, als Additiv für Zement und als Zusatzmittel zu hochviskosen Flüssigkeiten, wie z.B. Erdöl zur Verbesserung des Fließverhaltens und zum schnelleren Transport, sowie als Bestandteil von Kosmetikartikeln.Polyvinyl alcohol copolymers, processes for the preparation of the hydrogels, and the use of the hydrogels as materials in the biomedical and pharmaceutical fields, for the production of contact lenses, for the controlled release of active substances, as a carrier material for inclusion - immobilized biocatalysts, as a carrier material for transition metal catalysts, as a material for the production of reactive membranes, as an additive to drilling fluids, as a displacer in oil production, as an additive for cement and as an additive to highly viscous liquids, such as Petroleum to improve the flow behavior and for faster transport, as well as a component of cosmetic articles.
Hydrogele sind Wasser enthaltende Gele auf der Basis hydrophiler Polymere, die als dreidimensionale Netzwerke vorliegen. Als Hydrogele sind diese Polymere in Wasser unlöslich, quellen aber unter weitgehender Formerhaltung bis zu einem Gleichgewichtsvolumen auf. Die Netzwerkbildung erfolgt vorwiegend über chemische Verknüpfung der einzelnen Polymerketten, ist aber auch physikalisch durch elektrostatische, hydrophobe oder Dipol/Dipol-Wechselwirkungen zwischen einzelnen Segmenten der Polymerketten möglich. Über die Wahl der zum Polymeraufbau verwendeten Monomeren, die Art der Vernetzung und die Vernetzungsdichte können gewünschte Eigenschaften der Hydrogele gezielt eingestellt werden. Die notwendige Hydrophilie der Polymeren vermitteln u.a.Hydrogels are water-containing gels based on hydrophilic polymers that exist as three-dimensional networks. As hydrogels, these polymers are insoluble in water, but swell up to an equilibrium volume while largely maintaining their shape. Networking takes place primarily via chemical linking of the individual polymer chains, but is also physically possible through electrostatic, hydrophobic or dipole / dipole interactions between individual segments of the polymer chains. The desired properties of the hydrogels can be set in a targeted manner via the choice of the monomers used for the polymer structure, the type of crosslinking and the crosslinking density. The necessary hydrophilicity of the polymers provides, among other things,
Hydroxy -, Carboxylat -, Sulfonat - oder Amid - Gruppen. Synthetische Hydrogele basieren u.a. auf Poly(meth)acrylsäuren, Poly(meth)acryiaten, Polyvinylpyrrolidon oder Polyvinylalkohol. Hydrogele sind im allgemein gut verträglich mit lebenden Geweben (Quelle: Römpp Lexikon Chemie - Version 2.0, Stuttgart/New York: Georg Thieme Verlag 1999).Hydroxy, carboxylate, sulfonate or amide groups. Synthetic hydrogels are based on on poly (meth) acrylic acids, poly (meth) acrylicates, polyvinylpyrrolidone or polyvinyl alcohol. Hydrogels are generally well compatible with living tissues (source: Römpp Lexikon Chemie - Version 2.0, Stuttgart / New York: Georg Thieme Verlag 1999).
Hydrogele auf der Basis von Polyvinylalkohol sind bekannt (vgl. US2003008396A1 , US2001029399A1 , US0006231605B1 , US0005981826A, WO2001044307A3, W01998050017A1 , Hassan, Christie M.; Peppas, Nikolaos, A.; Advances in Polymer Science .(2000), 153 (Biopolymers, PVA Hydrogels Anionic PolymerisationHydrogels based on polyvinyl alcohol are known (cf. US2003008396A1, US2001029399A1, US0006231605B1, US0005981826A, WO2001044307A3, W01998050017A1, Hassan, Christie M .; Peppas, Nikolaos, A .; Advances in Polymer Science. (2000, 153, 153), Polymer Hydrogel Anionic Polymerization
Nanocomposites), 37-65., Peppas, Nikolaos A. , Hydrogels Med. Pharm. (1987), 2, 1-48. und dort zitierte Literatur.). Hydrogele auf der Basis von Polyvinylalkohol können durch unterschiedliche Methoden hergestellt werden, wie beispielsweise durch wiederholtes Einfrieren und . Auftauen einer wäßrigen Lösung von Polyvinylalkohol, durch Einwirkung ionisierender Strahlung (UV-Licht, gamma- Strahlung) auf eine wäßrige Lösung von Polyvinylalkohol, und durch Reaktion von Polyvinylalkohol mit vernetzenden Reagenzien wie Glutaraldehyd, Acetaldehyd, Formaldehyd, Maleinsäure, Oxalsäure, Alginsäure, Dimethylhamstoff, Glyoxal, Salzsäure, Polyacrolein, Diisocyanaten und/oder Divinylsulfat.Nanocomposites), 37-65., Peppas, Nikolaos A., Hydrogels Med. Pharm. (1987), 2, 1-48. and literature cited there.). Hydrogels based on polyvinyl alcohol can be produced by various methods, such as, for example, by repeated freezing and. Thawing an aqueous solution of Polyvinyl alcohol, by the action of ionizing radiation (UV light, gamma radiation) on an aqueous solution of polyvinyl alcohol, and by reaction of polyvinyl alcohol with cross-linking reagents such as glutaraldehyde, acetaldehyde, formaldehyde, maleic acid, oxalic acid, alginic acid, dimethyl urea, glyoxal, hydrochloric acid, polyacrolein , Diisocyanates and / or divinyl sulfate.
Hydrogele auf der Basis von Polyvinylalkoholen werden in der Regel aus konventionellem, linearen Polyvinylalkohol hergestellt. Hierbei tritt eine Trübung des Hydrogels durch kristalline Bereiche auf, welche dazu führt, daß die Hydrogele aus konventionellem Polyvinylalkohol nur bedingt für optische Anwendungen, wie beispielsweise Kontaktlinsen, geeignet sind. Desweiteren erhalten Hydrogele aus konventionellem Polyvinylalkohol ihre mechanischen Eigenschaften erst bei der Vernetzung zum Hydrogel.Hydrogels based on polyvinyl alcohol are usually made from conventional, linear polyvinyl alcohol. This causes the hydrogel to become cloudy due to crystalline areas, which means that the hydrogels made from conventional polyvinyl alcohol are only suitable for optical applications, such as contact lenses, to a limited extent. Furthermore, hydrogels made from conventional polyvinyl alcohol only acquire their mechanical properties when they are crosslinked to form the hydrogel.
Überraschenderweise wurde nun gefunden, daß Hydrogele aus Polyvinylalkoholen mit speziellen Geometrien, wie beispielsweise sternförmigen Geometrien, wie sie in DE10343607 (Schulte et al. / Celanese Ventures GmbH) und DE10356574 (Bruckmann et al. / Celanese Ventures GmbH) beschrieben sind, einen geringeren Mikrokristallinitätsgrad im Hydrogel hervorrufen, was zu verbesserten optischen Eigenschaften führt, und verbesserte mechanische Eigenschaften aufweisen.Surprisingly, it has now been found that hydrogels made of polyvinyl alcohols with special geometries, such as, for example, star-shaped geometries, as described in DE10343607 (Schulte et al. / Celanese Ventures GmbH) and DE10356574 (Bruckmann et al. / Celanese Ventures GmbH), have a lower degree of microcrystallinity in the hydrogel, which leads to improved optical properties and improved mechanical properties.
Desweiteren führt die spezielle Geometrie der Polyvinylalkohole durch eine Vernetzung der Polymere vor der Hydrogel-Bildung zu einem verringerten Abrieb.Furthermore, the special geometry of the polyvinyl alcohols leads to reduced abrasion by crosslinking the polymers before the hydrogel is formed.
Gegenstand der vorliegenden Erfindung sind somit Hydrogele enthaltend mindestens ein Polyvinylalkohol-Stempolymer.The present invention thus relates to hydrogels containing at least one polyvinyl alcohol stamp polymer.
Im Rahmen der vorliegenden Erfindung werden unter Hydrogelen enthaltend mindestens ein Polyvinylalkohol-Stempolymer sowohl Hydrogele, bei denen als Polymer exklusiv ein oder mehrere Polyvinylalkohol-Stempolymere eingesetzt werden, als auch Mischungen zwischen Polyvinylalkohol-Sternpolymeren mit anderen Polymeren verstanden. Besonders bevorzugt sind hierbei Mischungen aus Polyvinylalkohol-Stempolymeren mit konventionellem Polyvinylalkohol im Verhältnis von 99:1 bis 1 :99. Desweiteren besonders bevorzugt sind Mischungen aus Polyvinylalkohol-Stempolymeren mit Polyacrylsäuren, Polymethacrylsäuren, Polyacrylaten, Polymethacrylaten und Polyvinylpyrrolidon im Verhältnis von 99:1 bisIn the context of the present invention, hydrogels containing at least one polyvinyl alcohol stem polymer are understood to mean both hydrogels in which one or more polyvinyl alcohol star polymers are used exclusively as a polymer, and also mixtures between polyvinyl alcohol star polymers with other polymers. Mixtures of polyvinyl alcohol stamp polymers with conventional polyvinyl alcohol in a ratio of 99: 1 to 1:99 are particularly preferred. Mixtures of polyvinyl alcohol stamp polymers with polyacrylic acids, polymethacrylic acids, polyacrylates, polymethacrylates and polyvinylpyrrolidone in a ratio of 99: 1 to are also particularly preferred
1 :99.1:99.
Die erfindungsgemäßen Hydrogele enthalten neben den vorstehend genannten Polyvinylalkohol-Stempolymeren, wie der Name bereits verdeutlicht, noch Wasser. Polyvinylalkohole mit speziellen Geometrien lassen sich über unterschiedliche Methoden herstellen, zum einen über eine Ubergangsmetall-katalysierte Herstellung von Polyvinylacetat, wie er in DE10238659 beschrieben ist, gefolgt von einer Verseifung, wie er in DE10343607 beschrieben, oder über eine Copolymerisation von Vinylacetat mit vernetzenden Comonomeren, gefolgt von einer Verseifung, wie er in DE10356574 beschrieben.The hydrogels according to the invention contain, in addition to the above-mentioned polyvinyl alcohol stamp polymers, as the name already shows, water. Polyvinyl alcohols with special geometries can be produced by different methods, on the one hand via a transition metal-catalyzed production of polyvinyl acetate as described in DE10238659, followed by saponification as described in DE10343607 or via a copolymerization of vinyl acetate with crosslinking comonomers, followed by saponification as described in DE10356574.
Im folgenden werden die in DE10343607 und DE10356574 beschriebenenPolyvinylalkohole und Polyvinylalkohol-Copolymere als Polyvinylalkohol-In the following, the polyvinyl alcohols and polyvinyl alcohol copolymers described in DE10343607 and DE10356574 are described as polyvinyl alcohol.
Sternpolymere bezeichnet.Star polymers called.
Unter Polyvinylalkohol-Stempolymeren gemäß DE10343607 und DE10356574 werden Verbindungen der Formel I, II und IIIPolyvinyl alcohol stamped polymers according to DE10343607 and DE10356574 include compounds of the formula I, II and III
Formel Formel II Formel III Formula Formula II Formula III
worin Pol für ein Polymer auf der Basis eines Polyvinylalkohols steht, besonders bevorzugt für ein Homo-.oder Copolymer auf der Basis von Polyvinylalkohol, ganz besonders bevorzugt Polyvinylalkohol, Polyvinylalkohol-Polyvinylacetat- Copolymer, Polyvinylalkohol-Polyethylen-Copolymer, Polyvinylalkohol- Polyvinylchlorid-Copolymer und Polyvinylalkohol-Polyacrylsäuremethylester- Copolymer, und ein Zentralatom bedeutet und ein Atom der 13. bis 16. Gruppe des Periodensystems der Elemente, bevorzugt Kohlenstoff, Silicium, Stickstoff, Phosphor, Sauerstoff oder Schwefel, besonders bevorzugt Kohlenstoff oder Silicium, ist, undwherein Pol stands for a polymer based on a polyvinyl alcohol, particularly preferably for a homo- or copolymer based on polyvinyl alcohol, very particularly preferably polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymer, polyvinyl alcohol-polyethylene copolymer, polyvinyl alcohol-polyvinyl chloride copolymer and Polyvinyl alcohol-polyacrylic acid methyl ester copolymer, and denotes a central atom and is an atom from the 13th to 16th group of the Periodic Table of the Elements, preferably carbon, silicon, nitrogen, phosphorus, oxygen or sulfur, particularly preferably carbon or silicon, and
X1 jeweils gleich oder verschieden ist, und ein Halogenatom, bevorzugt Fluor, Chlor, Brom oder lod, besonders bevorzugt Chlor, Brom oder lod ist, undX 1 is in each case the same or different, and is a halogen atom, preferably fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine, and
R1 gleich oder verschieden ist, und gleich Wasserstoff oder eine C-i - C20- kohlenstoffhaltige Gruppe ist, undR 1 is the same or different and is hydrogen or a Ci - C 20 carbon-containing group, and
R^ gleich oder verschieden ist und eine verbrückende Ci - C20 -kohlenstoffhaltige Gruppe zwischen dem Zentralatom Z und der initiierenden Einheit [R3-X1] oder Silicium oder Sauerstoff bedeutet, und R3 gleich oder verschieden ist und Kohlenstoff oder Silicium bedeutet, undR ^ is the same or different and is a bridging Ci - C 20 carbon-containing group between the central atom Z and the initiating unit [R 3 -X 1 ] or silicon or oxygen, and R 3 is the same or different and means carbon or silicon, and
R4 gleich oder verschieden ist und ein Wasserstoffatom oder eine Ci - C20 - kohlenstoffhaltige Gruppe ist, undR 4 is the same or different and is a hydrogen atom or a Ci - C 20 carbon-containing group, and
R5 gleich oder verschieden ist und Wasserstoff oder eine Ci - C20 - kohlenstoffhaltige Gruppe bedeutet,R 5 is identical or different and denotes hydrogen or a Ci - C 20 carbon-containing group,
I eine ganze natürliche Zahl ist und für Null, 1 , 2 oder 3 steht, und m jeweils gleich oder verschieden ist und eine ganze natürlich Zahl ist und für Null, 1 , 2, 3, 4 und 5 steht, und n jeweils gleich oder verschieden ist und eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, und o jeweils gleich oder verschieden ist und 1 oder 2 ist, und p jeweils gleich oder verschieden ist und eine ganze natürliche Zahl ist und für 1 , 2, 3, 4 und 5 steht, und q eine ganze natürliche Zahl ist und für 2, 3 und 4 steht, undI is a whole natural number and stands for zero, 1, 2 or 3, and m is in each case identical or different and is a whole natural number and stands for zero, 1, 2, 3, 4 and 5, and n each is equal to or is different and is an integer and for zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 and 20 is and o is the same or different and is 1 or 2, and p is the same or different and is an integer and is 1, 2, 3, 4 and 5, and q is an integer and stands for 2, 3 and 4, and
Ar ein aromatisches Grundgerüst mit mindestens vier Kohlenstoffatomen ist, bei dem ein oder mehrere C-Atome durch Bor, Stickstoff oder Phosphor ausgetauscht sein können, und wobei bevorzugte aromatische oder heteroaromatische Grundgerüste sich von Benzol, Biphenyl, Naphthalin, Anthracen, Phenanthren, Triphenylen, Chinolin, Pyridin, Bipyridin, Pyridazin, Pyrimidin, Pyrazin, Triazin, Benzopyrrol, Benzotriazol, Benzopyridin, Benzopyrazidin, Benzopyrimidin, Benzopyrazin, Benzotriazin, Indolizin, Chinolizin, Carbazol, Acridin, Phenazin, Benzochinolin, Phenoxazin, die gegebenenfalls auch substituiert sein können, ableiten, und y eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, und z eine ganze natürliche Zahl ist und für 2, 3, 4, 5, 6, 7, 8, 9 und 10 steht.Ar is an aromatic backbone with at least four carbon atoms, in which one or more carbon atoms can be replaced by boron, nitrogen or phosphorus, and preferred aromatic or heteroaromatic backbones are derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, quinoline , Pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, which may also be substituted, which may also be substituted and y is an integer and is zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 and z is an integer and is 2, 3, 4, 5, 6, 7, 8, 9 and 10.
Ap ein cyclisches nicht-aromatisches Grundgerüst mit mindestens drei Kohlenstoffatomen ist, welches auch Heteroatome wie Stickstoff, Bor, Phosphor, Sauerstoff oder Schwefel enthalten kann, ist, wobei sich bevorzugte aliphatische Grundgerüste aus der Gruppe Cycloalkyl, wie beispielsweise Cyciopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, oder aus der Gruppe Cycloheteroalkyl, wie beispielsweise Aziridin, Azetidin, Pyrrolidin, Piperidin, Azepan, Azocan, 1 ,3,5-Triazinan, 1 ,3,5- Trioxan, Oxetan, Furan, Dihydrofuran, Tetrahydrofuran, Pyran, Dihydropyran, ' Tetrahydropyran, Oxepan, Oxocan, oder aus der Gruppe der Saccharide, wie beispielsweise alpha-Glucose, beta-Glucose, ableiten lassen, und a eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, und b eine ganze natürliche Zahl ist und für 2, 3, 4, 5, 6, 7, 8, 9 und 10 steht, und c eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, d gleich oder verschieden sein kann, und Null oder Eins ist, verstanden, sowieAp is a cyclic non-aromatic backbone with at least three carbon atoms, which can also contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, preferred aliphatic backbones from the group cycloalkyl, such as, for example, cyciopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, Cyclooctyl, Cyclononyl, or from the group cycloheteroalkyl, such as, for example, aziridine, azetidine, pyrrolidine, piperidine, azepane, azocane, 1, 3,5-triazinane, 1, 3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran , Pyran, Dihydropyran, ' Tetrahydropyran, Oxepan, Oxocan, or from the group of saccharides, such as alpha-glucose, beta-glucose, can be derived, and a is an integer and is zero, 1, 2, 3, 4 , 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 and 20, and b is an integer and is 2, 3, 4, 5, 6, 7, 8, 9 and 10, and c is an integer and is zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 and 20 stands, d can be the same or different, and is zero or one, understood, as well
Polyvinylalkohol-Copolymere auf der Basis von Polyvinylester-Copolymeren sind durch ein Verfahren umfassend die Schritte: A) Radikalische Lösungs- oder Massen-Polymerisation von Vinylestem in Gegenwart eines Radikalbildners und gegebenenfalls in Gegenwart eines Radikalfängers, B) Zugabe einer zur Vernetzung befähigten Polyalkenyl-Verbindung, C) gegebenenfalls Aufarbeitung und Isolierung der gebildeten Polyvinylester- Copolymere, D) Verseifung der in B) hergestellten Polyvinylester/Polyvinylester-polyalken- Mischung oder der unter C) isolierten Polyvinylester-polyalken- Copolymere mit Base unter Ausbildung der PolyvinylalkohoiyPolyvinylalkohol-polyalken-Mischungen bzw. Polyvinylalkohol-polyälken-Copolymeren und Isolierung der Produkte,Polyvinyl alcohol copolymers based on polyvinyl ester copolymers are by a method comprising the steps of: A) radical solution or bulk polymerization of vinyl esters in the presence of a radical generator and, if appropriate, in the presence of a radical scavenger, B) addition of a polyalkenyl compound capable of crosslinking , C) optionally working up and isolation of the polyvinyl ester copolymers formed, D) saponification of the polyvinyl ester / polyvinyl ester-polyalkene mixture produced in B) or of the polyvinyl ester-polyalkene copolymers isolated under C) with the formation of the polyvinyl alcohol-polyvinyl alcohol-polyalkene mixtures or Polyvinyl alcohol-polyalkene copolymers and insulation of the products,
dadurch gekennzeichnet, daß es sich bei. den in Schritt B) eingesetzten Polyalkenyl-characterized in that it is. the polyalkenyl used in step B)
Verbindungen um Verbindungen gemäß Formel IV:Compounds by compounds according to formula IV:
Formel IV worin: R6 eine Cβ - C2o-Arylgruppe, eine C5 - C2o-Heteroarylgruppe, eine C4-C2o- Cycloalkylgruppe, eine C -C20-Heterocycloalkylgruppe oder eine C1 - C20- Alkylgruppe bedeutet, bei der ein oder mehrere nicht direkt benachbarte C- Atome durch ein Element der 5. oder 6. Gruppe der Elemente, bevorzugt Stickstoff, Phosphor, Sauerstoff oder Schwefel, besonders bevorzugt Stickstoff oder Sauerstoff, ersetzt sein können, undFormula IV wherein: R 6 is a Cβ - C 2 o aryl group, a C5 - C 2 o heteroaryl group, a C 4 -C 2 o cycloalkyl group, a C -C 20 heterocycloalkyl group or a C 1 - C 20 alkyl group means in which one or more non-directly adjacent C atoms can be replaced by an element of the 5th or 6th group of elements, preferably nitrogen, phosphorus, oxygen or sulfur, particularly preferably nitrogen or oxygen, and
R7 gleich oder verschieden ist, und gleich Wasserstoff, Sauerstoff, Schwefel oder eine Hydroxygruppe, eine Carbamoylgruppe, eine Aminogruppe, eine Carboxygruppe, eine Ci - C20 -Alkylcarbonylgruppe, eine Ci - C20 - Alkyloxygruppe, eine C6 - C20 -Aryloxygruppe, eine Iminogruppe, eine Ci - C2o -Alkyliminogruppe, eine C6 - C20 -Alkyliminogruppe, eine Cyanogruppe, eine Ci - C2o - Alkylgruppe, eine Cβ - C2o -Arylgruppe, eine C5 - C2o - Heteroarylgruppe, eine C4-C20-Cycloalkylgruppe, eine C4-C2o-Heterocycloalkyl eine C7 - C2o-Alkylarylgruppe, eine C7 - C3o-Arylalkylgruppe, eine C2 - C-20- Alkenylgruppe, eine C2 - C20 - α-Oxy-alkenyl, eine halogenhaltige Ci - C20- Alkylgruppe, eine C6 - C2o -Arylgruppe, eine C7 - C2o-Alkylarylgruppe, eine C7 - C30-Arylalkylgruppe oder eine C2 - C2o-Alkenylgruppe bedeutet, und R8, R9, R10 gleich oder verschieden sind, und gleich Wasserstoff oder eine Ci - C2o - kohlenstoffhaltige Gruppe ist, und e eine ganze natürliche Zahl von 0 bis 40 bedeutet, handelt, erhältlich.R 7 is the same or different and is hydrogen, oxygen, sulfur or a hydroxy group, a carbamoyl group, an amino group, one Carboxy group, a Ci - C 20 alkylcarbonyl group, a Ci - C 20 alkyloxy group, a C 6 - C 20 aryloxy group, an imino group, a Ci - C 2 o alkylimino group, a C 6 - C 20 alkylimino group, a cyano group , a Ci - C 2 o - alkyl group, a Cβ - C 2 o aryl group, a C 5 - C 2 o - heteroaryl group, a C 4 -C 20 cycloalkyl group, a C 4 -C 2 o heterocycloalkyl a C 7 - C 2 o -alkylaryl group, a C 7 - C 3 o-arylalkyl group, a C 2 - C- 2 O-alkenyl group, a C 2 - C 20 - α-oxy-alkenyl, a halogen-containing Ci - C 20 alkyl group, represents a C 6 - C 2 o aryl group, a C 7 - C 2 o alkylaryl group, a C 7 - C 30 arylalkyl group or a C 2 - C 2 o alkenyl group, and R 8 , R 9 , R 10 are the same or are different, and are hydrogen or a Ci - C 2 o - carbon-containing group, and e is an integer from 0 to 40, is available.
Im Rahmen der vorliegenden Erfindung werden unter einer Ci - C2o-kohlenstoff- haltigen Gruppe bevorzugt die Reste C C2o-Alkyl, besonders bevorzugt Methyl,In the context of the present invention, the residues CC 2 o-alkyl, particularly preferably methyl, are preferably selected from a group containing C 1 -C 2 o-carbon,
Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, s-Butyl, t-Butyl, n-Pentyl, s-Pentyl, Cyclopentyl, n-Hexyl, Cyclohexyl, n-Octyl oder Cyclooctyl, Ci - C20 - Alkenyl, besonders bevorzugt Ethenyl, Propenyi, Butenyl, Pentenyl, Cyclopentenyl, Hexenyl, Cyclohexenyl, Octenyl oder Cyclooctenyl, Ci - C2o - Alkinyl, besonders bevorzugt Ethinyl, Propinyl, Butinyl, Pentinyl, Hexinyl oder Octinyl, C6-C2o-Aryl, besonders bevorzugt Phenyl, Biphenyl, Naphthyl oder Anthracenyl, Ci - C20 - Fluoralkyl, besonders bevorzugt Trifluormethyl, Pentafluorethyl oder 2,2,2-Trifluorethyl, C6-C2o- Aryl, besonders bevorzugt Phenyl, Biphenyl, Naphthyl, Anthracenyl, Triphenylenyl, [1 ,1';3',1 "]Terphenyl-2'-yl, Binaphthyl oder Phenanthrenyl, C6-C2o-Fluoraryl, besonders bevorzugt Tetrafluorop enyl oder Heptafluoronaphthyl, Cι-C20-Alkoxy, besonders bevorzugt Methoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s- Butoxy oder t-Butoxy, C6-C2o-Aryloxy, besonders bevorzugt Phenoxy, Naphthoxy, Biphenyloxy, Anthracenyloxy, Phenanthrenyloxy, C7-C20-Arylalkyl, besonders bevorzugt o-Tolyl, m-Tolyl, p-Tolyl, 2,6-Dimethylphenyl, 2,6-Diethylphenyl, 2,6-Di-i- propylphenyl, 2,6-Di-t-butylphenyl, o-t-Butylphenyl, m-t-Butylphenyl, p-t-Butylphenyl,Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, Ci - C 20 - alkenyl, particularly preferably ethenyl, propenyi, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, octenyl or cyclooctenyl, Ci - C 2 o - alkynyl, particularly preferably ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl, C6 - C 2 o-aryl, particularly preferably phenyl, biphenyl, naphthyl or anthracenyl, Ci - C 20 - fluoroalkyl, particularly preferably trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl, C 6 -C 2 o-aryl, particularly preferably phenyl, biphenyl , Naphthyl, anthracenyl, triphenylenyl, [1, 1 ';3', 1 "] terphenyl-2'-yl, binaphthyl or phenanthrenyl, C 6 -C 2 o-fluoroaryl, particularly preferably tetrafluoropenyl or heptafluoronaphthyl, Cι-C 20 Alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy, C 6 -C 2 o-aryloxy, particularly preferably phenoxy, naphthoxy, biphen yloxy, anthracenyloxy, phenanthrenyloxy, C 7 -C 20 arylalkyl, particularly preferably o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-i-propylphenyl, 2,6-di-t-butylphenyl, ot-butylphenyl, mt-butylphenyl, pt-butylphenyl,
C7-C2o-Alkylaryl, besonders bevorzugt Benzyl, Ethylphenyl, Propylphenyl, Diphenylmethyl, Triphenylmethyl oder Naphthalinylmethyl, C7-C2o-Aryloxyalkyl, besonders bevorzugt o-Methoxyphenyl, m-Phenoxymethyl, p-Phenoxymethyl, C12- C2o-Aryloxyaryl, besonders bevorzugt p-Phenoxyphenyl, C5-C2o-Heteroaryl, besonders bevorzugt 2-Pyridyl, 3-Pyridyl, 4-Pyridyl, Chinolinyl, Isochinolinyl,C 7 -C 2 o-alkylaryl, particularly preferably benzyl, ethylphenyl, propylphenyl, diphenylmethyl, triphenylmethyl or naphthalinylmethyl, C 7 -C 2o-aryloxyalkyl, particularly preferably o-methoxyphenyl, m-phenoxymethyl, p-phenoxymethyl, C 12 - C2o-aryloxyaryl , particularly preferably p-phenoxyphenyl, C 5 -C 2 o-heteroaryl, particularly preferably 2-pyridyl, 3-pyridyl, 4-pyridyl, quinolinyl, isoquinolinyl,
Acridinyl, Benzochinolinyl oder Benzoisochinolinyl, C4-C2o-Heterocycloalkyl, besonders bevorzugt Furyl, Benzofuryl, 2-Pyrolidinyl, 2-lndolyl, 3-lndolyl, 2,3- Dihydroindolyl, C8-C2o-Arylalkenyl, besonders bevorzugt o-Vinylphenyl, m- Vinylphenyl, p-Vinylphenyl, C8-C2o-Arylalkinyl, besonders bevorzugt o-Ethinylphenyl, m-Ethinylphenyl oder p-Ethinylphenyl, C2 - C20 - heteroatomhaltige Gruppe, besonders bevorzugt Carbonyl, Benzoyl, Oxybenzoyl, Benzoyloxy, Acetyl, Acetoxy oder Nitril verstanden, wobei eine oder mehrere C-ι-C2o-kohlenstoffhaltige Gruppen ein cyclisches System bilden können.Acridinyl, benzoquinolinyl or benzoisoquinolinyl, C 4 -C 2 o-heterocycloalkyl, particularly preferably furyl, benzofuryl, 2-pyrolidinyl, 2-indolyl, 3-indolyl, 2,3-dihydroindolyl, C 8 -C 2 o-arylalkenyl, particularly preferred o-vinylphenyl, m-vinylphenyl, p-vinylphenyl, C 8 -C 2 o-arylalkynyl, particularly preferably o-ethynylphenyl, m-Ethynylphenyl or p -ethynylphenyl, C 2 - C 20 - heteroatom-containing group, particularly preferably carbonyl, benzoyl, oxybenzoyl, benzoyloxy, acetyl, acetoxy or nitrile understood, where one or more C-ι-C 2 o-carbon-containing groups is a cyclic Can form a system.
Im Rahmen der vorliegenden Erfindung werden unter einer verbrückenden Ci - C2o - kohlenstoffhaltigen Gruppe bevorzugt Cι-C2o-Alkyl, besonders bevorzugt Methylen, Ethylen, Propylen, Butylen, Pentylen, Cyclopentylen, Hexylen oder Cyclohexylen, d- C2o-Alkenyl, besonders bevorzugt Ethenyl, Propenyi, Butenyl, Pentenyl, Cyclopentenyl, Hexenyl oder Cyclohexenyl, Cι-C2o-Alkinyl, besonders bevorzugtIn the context of the present invention, a bridging C 1 -C 2 -carbon-containing group is preferably C 1 -C 2 -alkyl, particularly preferably methylene, ethylene, propylene, butylene, pentylene, cyclopentylene, hexylene or cyclohexylene, d- C 2 o- Alkenyl, particularly preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl or cyclohexenyl, C 1 -C 2 -alkynyl, particularly preferred
Ethinyl, Propinyl, Butinyl, Pentinyl oder Hexinyl, CrC2o-Aryl, besonders bevorzugt o- Phenylen, m-Phenylen oder p-Phenylen, C^ - C20 - heteroatomhaltige Gruppe, besonders bevorzugt Carbonyl, Oxycarbonyl, Carbonyloxy, Carbamoyl oder Amido verstanden.Ethynyl, propynyl, butynyl, pentynyl or hexynyl, CrC 2 o-aryl, particularly preferably o-phenylene, m-phenylene or p-phenylene, C ^ - C 20 - heteroatom-containing group, particularly preferably carbonyl, oxycarbonyl, carbonyloxy, carbamoyl or amido Roger that.
Weiterer Gegenstand der vorliegenden Erfindung ist die Herstellung und die Verwendung der erfindungsgemäßen Hydrogele.Another object of the present invention is the production and use of the hydrogels according to the invention.
Die Herstellung der erfindungsgemäßen Hydrogele enthaltend ein Polyvinylalkohol- Sternpolymer kann beispielsweise durch:The hydrogels according to the invention containing a polyvinyl alcohol star polymer can be prepared, for example, by:
• wiederholtes Einfrieren und Auftauen einer wäßrigen Lösung enthaltend ein Polyvinylalkohol-Stempolymer und optional weitere Komponenten,Repeated freezing and thawing of an aqueous solution containing a polyvinyl alcohol stamping polymer and optionally further components,
• Einwirkung ionisierender Strahlung (UV-Licht, gamma-Strahlung) auf eine wäßrige Lösung enthaltend ein Polyvinylalkohol-Stempolymer und optional weitere Komponenten und• Exposure to ionizing radiation (UV light, gamma radiation) on an aqueous solution containing a polyvinyl alcohol stamping polymer and optionally further components and
• Reaktion in wäßriger Lösung enthaltend ein Polyvinylalkohol-Stempolymer und optional weitere Komponenten mit vernetzenden Reagenzien wie beispielsweise Glutaraldehyd, Acetaldehyd, Formaldehyd, Maleinsäure, Oxalsäure, Alginsäure, Dimethylharnstoff, Glyoxal, Salzsäure, Polyacrolein, Diisocyanaten und/oder Divinylsulfat, gegebenenfalls unter Säure- oder Base-Katalyse, erfolgen. Unter weiteren Komponenten werden unter anderem:• Reaction in aqueous solution containing a polyvinyl alcohol stamping polymer and optionally further components with cross-linking reagents such as glutaraldehyde, acetaldehyde, formaldehyde, maleic acid, oxalic acid, alginic acid, dimethyl urea, glyoxal, hydrochloric acid, polyacrolein, diisocyanates and / or divinyl sulfate, optionally under acid or Base catalysis. Other components include:
• konventioneller Polyvinylalkohol,Conventional polyvinyl alcohol,
• andere Polymere wie beispielsweise Polyacrylsäuren, Polymethacrylsäuren, Polyacrylaten, Polymethacrylaten und Polyvinylpyrrolidon,Other polymers such as, for example, polyacrylic acids, polymethacrylic acids, polyacrylates, polymethacrylates and polyvinylpyrrolidone,
• Mikroorganismen,• microorganisms,
• Alginsäure-Derivate, wie beispielsweise Natriumalginat, • Salze, wie beispielsweise Natriumcarbonat, Kaliumcarbonat, Calciumcarbonat, Ammoniumcarbonat, Magnesiumcarbonat, Natriumhydrogencarbonat, Kaliumhydrogencarbonat, Calciumhydrogencarbonat, Magnesiumhydrogencarbonat, Natriumsulfat, Kaliumsulfat, Ammoniumsulfat, Magnesiumsulfat, Natriumphosphat, Kaliumphosphat, Ammoniumphosphat, Magnesiumphosphat, Natriumchlorid, Kaliumchlorid, Ammoniumchlorid, Calciumchlorid, Magnesiumchlorid und/oder Aluminiumchlorid verstanden.Alginic acid derivatives, such as sodium alginate, Salts such as sodium carbonate, potassium carbonate, calcium carbonate, ammonium carbonate, magnesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydrogen carbonate, sodium sulfate, potassium sulfate, ammonium sulfate, magnesium sulfate, sodium phosphate, potassium phosphate, ammonium phosphate, magnesium phosphate, sodium chloride, potassium chloride, ammonium chloride and calcium chloride, calcium chloride, calcium chloride or understood aluminum chloride.
Die erfindungsgemäßen Hydrogele zeichnen sich gegenüber Hydrogelen aus konventionellen Polymeren durch eine höherer Klarheit aus (Vergleich der Haze- Werte: Siehe Beispiele 3 und 4).The hydrogels according to the invention are distinguished from hydrogels from conventional polymers by a higher degree of clarity (comparison of the haze values: see examples 3 and 4).
Die erfindungsgemäßen Hydrogele zeichnen sich gegenüber Hydrogelen aus konventionellen Polymeren durch eine höhere Beständigkeit gegenüber Wasser aus, was bei einem Einsatz als Trägermaterial für Einschluß - immobilisierte Biokatalysatoren, beispielsweise für die Abwasserbehandlung, von Vorteil ist (Vergleich der Beständigkeit gegenüber Wasser: Siehe Beispiele 7 und 8).The hydrogels according to the invention are distinguished from hydrogels from conventional polymers by a higher resistance to water, which is advantageous when used as a carrier material for inclusion-immobilized biocatalysts, for example for wastewater treatment (comparison of resistance to water: see examples 7 and 8 ).
Erläuternde, die Erfindung jedoch nicht einschränkende Beispiele für die erfindungsgemäßen Hydrogele sind Produkte aus Mischungen von:Illustrative but non-limiting examples of the hydrogels according to the invention are products made from mixtures of:
• Polyvinylalkohol-Sternpolymer(en) und Wasser,Polyvinyl alcohol star polymer (s) and water,
• Polyvinylalkohol-Sternpolymer(en), konventionellem Polyvinylalkohol und Wasser,Polyvinyl alcohol star polymer (s), conventional polyvinyl alcohol and water,
• Polyvinylalkohol-Sternpolymer(en), Polyacrylsäure und Wasser • Polyvinylalkohol-Sternpolymer(en), Polymethacrylsäuren und Wasser• Polyvinyl alcohol star polymer (s), polyacrylic acid and water • Polyvinyl alcohol star polymer (s), polymethacrylic acids and water
• Polyvinylalkohol-Sternpolymer(en), Polyacrylaten und Wasser• Polyvinyl alcohol star polymer (s), polyacrylates and water
• Polyvinylalkohol-Sternpolymer(en), Polymethacrylaten und Wasser• Polyvinyl alcohol star polymer (s), polymethacrylates and water
• Polyvinylalkohol-Stempolymer(en), Polyvinylpyrrolidon und Wasser• Polyvinyl alcohol stamp polymer (s), polyvinyl pyrrolidone and water
• Polyvinylalkohol-Stempolymer(en), konventionellem Polyvinylalkohol, Natriumalginat, Calciumchlorid, Formaldehyd und Wasser,Polyvinyl alcohol stamp polymer (s), conventional polyvinyl alcohol, sodium alginate, calcium chloride, formaldehyde and water,
• Polyvinylalkohol-Sternpolymer(en), konventionellem Polyvinylalkohol, Mikroorganismen und Wasser,Polyvinyl alcohol star polymer (s), conventional polyvinyl alcohol, microorganisms and water,
• Polyvinylalkohol-Sternpolymer(en), konventionellem Polyvinylalkohol, Calciumchlorid und Wasser, • Polyvinylalkohol-Stempolymer(en), konventionellem Polyvinylalkohol, Calciumchlorid, Mikroorganismen und Wasser. Weiterer Gegenstand der Erfindung ist die Verwendung des Hydrogels enthaltend ein oder mehrere Polyvinylalkohol-Sternpolymer(e) als: • Materialien im biomedizinischen und pharmazeutischen Bereich, beispielsweise als künstliches Gewebe oder zur Wundbehandlung als Material zur Herstellung von Kontaktlinsen als Material zur kontrollierten Freisetzung von Wirkstoffen als Trägermaterial für Einschluß - immobilisierte Biokatalysatoren, beispielsweise für die Abwasserbehandlung als Trägermaterial für Übe.rgangsmetallkatalysatoren, beispielsweise Palladiumkatalysatoren als Material für die Herstellung von Reaktivmembranen, als Zusatz zu Bohrflüssigkeiten, insbesondere, aufgrund der Abbaubarkeit, als Zusatz zu Bohrspülungen für Offshore-Applikationen als Verdrängungsmittel bei der Ölförderung als Additiv für Zement als Zusatzmittel zu hochviskosen Flüssigkeiten, wie z.B. Erdöl zur Verbesserung des Fließverhaltens und zum schnelleren Transport als Bestandteil von Kosmetikartikeln.• polyvinyl alcohol star polymer (s), conventional polyvinyl alcohol, calcium chloride and water, • polyvinyl alcohol star polymer (s), conventional polyvinyl alcohol, calcium chloride, microorganisms and water. Another object of the invention is the use of the hydrogel containing one or more polyvinyl alcohol star polymer (s) as: • Materials in the biomedical and pharmaceutical fields, for example as artificial tissue or for wound treatment as material for the production of contact lenses as material for the controlled release of active substances as Carrier material for inclusion - immobilized biocatalysts, for example for wastewater treatment as a carrier material for transition metal catalysts, for example palladium catalysts as material for the production of reactive membranes, as an additive to drilling fluids, in particular, due to the degradability, as an additive to drilling fluids for offshore applications as a displacement agent Oil production as an additive for cement as an additive to highly viscous liquids such as petroleum to improve the flow behavior and for faster transport as a component of cosmetic products Pedal.
Die Erfindung wird durch folgende, die Erfindung jedoch nicht einschränkendeThe invention is illustrated by the following, but not limiting, the invention
Beispiele erläutert.Examples explained.
Beispiel 1 : Herstellung eine Polyvinylalkohol-Stempolymers gemäß DE10343607Example 1: Preparation of a polyvinyl alcohol stem polymer according to DE10343607
In einem 1000 ml Rundkolben werden 167 ml einer 1 %igen methanolischen Natronlauge im Wasserbad auf 50°C erwärmt. Hierzu wird über einen Zeitraum von 30 min. eine Lösung von 50 g Polyvinylacetat-Stempolymer (hergestellt gemäß DE10238659) in 333 ml Methanol zugetropft. Nach Beendigung der Zugabe wird noch 30 min. gerührt. Der weiße Niederschlag wird abfiltriert, mit Methanol alkalifrei gewaschen, und im Vakuum getrocknet. Ausbeute: 25.0 g. 1H-NMR (500 MHz, [D6]- DSMO): δ = 6.65 (s, aromat. H), 4.65, 4.46, 3.89, 3.84, 3.31 , 1 .44 - 1 .33 (4 x s, 1 x m, PVOH) ppm. Beispiel 2: Herstellung eine Polyvinylalkohol-Sternpolymers gemäß DE10356574In a 1000 ml round-bottom flask, 167 ml of a 1% methanolic sodium hydroxide solution are heated to 50 ° C. in a water bath. For this, over a period of 30 min. a solution of 50 g of polyvinyl acetate stamp polymer (prepared according to DE10238659) in 333 ml of methanol was added dropwise. After the addition has ended, a further 30 min. touched. The white precipitate is filtered off, washed with methanol free of alkali and dried in vacuo. Yield: 25.0 g. 1 H-NMR (500 MHz, [D 6 ] - DSMO): δ = 6.65 (s, aromatic H), 4.65, 4.46, 3.89, 3.84, 3.31, 1.44 - 1.33 (4 xs, 1 xm , PVOH) ppm. Example 2: Preparation of a polyvinyl alcohol star polymer according to DE10356574
132 ml (1.43 mol) Vinylacetat, 9.0 g (70.2 mmol) Diallylformai, 1.6 ml (7.3 mmol) Tris- (2,2,2-trifluorethylphosphit und 1.25 g (3.6 mmol) Dibenzoylperoxid (70 % ig, Rest: H20) werden in 68 ml Toluol vorgelegt. Die klare farblose Lösung wird 20 h bei 70°C gerührt. Die flüchtigen Bestandteile werden im Ölpumpenvakuum entfernt und das Polyvinylacetat-Sternpolymer wird in 200 ml Methanol aufgenommen. Diese Lösung wird innerhalb von 15 min. zu 400 ml einer 1%igen NaOH-Lösung in Methanol zugetropft. Es wird noch 90 min. bei 50°C gerührt. Der Polyvinylalkohol wird abfiltriert, mit Methanol neutral gewaschen und im Ölpumpenvakuum getrocknet.132 ml (1.43 mol) of vinyl acetate, 9.0 g (70.2 mmol) of diallylformai, 1.6 ml (7.3 mmol) of tris- (2,2,2-trifluoroethylphosphite and 1.25 g (3.6 mmol) of dibenzoyl peroxide (70%, remainder: H 2 0 ) are placed in 68 ml of toluene, the clear colorless solution is stirred for 20 h at 70 ° C. The volatile constituents are removed in an oil pump vacuum and the polyvinyl acetate star polymer is taken up in 200 ml of methanol ml of a 1% NaOH solution in methanol is added dropwise, and the mixture is stirred for a further 90 minutes at 50 ° C. The polyvinyl alcohol is filtered off, washed neutral with methanol and dried in an oil pump vacuum.
Ausbeute: 14.4 g (22 %) 1H-NMR (500 MHz, [D6]-DSMO): δ = 5.92 - 5.87 (m), 5.24, 5.13 (2 x d), 4.66, 4.61 , 4.46, 4.22, 4.21, 4.10, 4.09, 4.00, 3.89, 3.84, 3.35, 3.16, 1.43 - 1.33 (13 x m) ppm.Yield: 14.4 g (22%) 1 H-NMR (500 MHz, [D 6 ] -DSMO): δ = 5.92 - 5.87 (m), 5.24, 5.13 (2 xd), 4.66, 4.61, 4.46, 4.22, 4.21 , 4.10, 4.09, 4.00, 3.89, 3.84, 3.35, 3.16, 1.43 - 1.33 (13 xm) ppm.
Beispiel 3: Herstellung eines Hydrogels enthaltend ein Polyvinylalkohol- StempolymerExample 3: Preparation of a hydrogel containing a polyvinyl alcohol stamp polymer
25 g Polyvinylalkohol-Stempolymer (Beispiel 1 ) werden bei 70°C in 75 ml demineralisiertem Wasser gelöst. Die Lösung wird in eine flache Metallschale (20 x 20 cm) gegeben, mit einem Deckel versehen und.12 h bei -30°C aufbewahrt. Danach läßt man die Lösung auf innerhalb von 12 h auf Raumtemperatur kommen und wiederholt den Einfrier - Auftau - Vorgang noch zweimal. Das Hydrogel wird in Form eine 0.25 cm dicken Filmes erhalten. Trübung (Haze-Wert in Prozent): 1.3.25 g of polyvinyl alcohol stamp polymer (Example 1) are dissolved at 70 ° C. in 75 ml of demineralized water. The solution is placed in a flat metal bowl (20 x 20 cm), covered with a lid and stored for 12 hours at -30 ° C. The solution is then allowed to come to room temperature within 12 h and the freeze-thaw process is repeated twice. The hydrogel is obtained in the form of a 0.25 cm thick film. Turbidity (Haze value in percent): 1.3.
Beispiel 4: Herstellung eines Hydrogels enthaltend einen linearen Polyvinylalkohol (Vergleichsbeispiel)Example 4: Preparation of a hydrogel containing a linear polyvinyl alcohol (comparative example)
25 g Polyvinylalkohol (Celvol 103 der Fa. Celanese) werden bei 70°C in 75 ml demineralisiertem Wasser gelöst. Die Lösung wird in eine flache Metallschale (20 x 20 cm) gegeben, mit einem Deckel versehen und 12 h bei -30°C aufbewahrt. Danach läßt man die Lösung auf innerhalb von 12 h auf Raumtemperatur kommen und wiederholt den Einfrier - Auftau - Vorgang noch zweimal. Das Hydrogel wird in Form eine 0.25 cm dicken Filmes erhalten. Trübung (Haze-Wert in Prozent): 4.6.25 g of polyvinyl alcohol (Celvol 103 from Celanese) are dissolved in 75 ml of demineralized water at 70 ° C. The solution is placed in a flat metal bowl (20 x 20 cm), covered with a lid and stored at -30 ° C for 12 h. The solution is then allowed to come to room temperature within 12 h and the freeze-thaw process is repeated twice. The hydrogel is obtained in the form of a 0.25 cm thick film. Turbidity (Haze value in percent): 4.6.
Beispiel 5: Herstellung eines Hydrogels enthaltend ein Gemisch eines Polyvinylalkohol-Sternpolymers mit einem linearen PolyvinylalkoholExample 5: Preparation of a hydrogel containing a mixture of a polyvinyl alcohol star polymer with a linear polyvinyl alcohol
2 g Polyvinylalkohol-Stempolymer (Beispiel 2), 2 g Polyvinylalkohol (Celvol 103 der Fa. Celanese), 0.5 g Alginsäure-Natriumsalz und 0.15 g Natriumhydrogencarbonat werden bei 70°C in 50 ml Wasser gelöst und nach Abkühlen auf Raumtemperatur zu 250 ml einer 0.1 molaren Caiciumchlorid-Lösung in großen Tropfen aus einer Spritze ohne Kanüle unter langsamem Rühren zugetropft, wobei sich ca. 3 mm große sphärische Partikel bilden. Die Partikel werden durch vorsichtige Filtration über eine Glasfritte isoliert und zu einer 40°C warmen Lösung von 5 g Formaldehyd (37 %ig in Wasser), 50 g konzentrierter Schwefelsäure und 25 g Natriumsulfat gegeben. Nach einer Stunde werden die verfestigten sphärischen Partikel durch Filtration isoliert und mit Wasser neutral gewaschen. Ausbeute: 43 g Hydrogel als sphärische Partikel.2 g of polyvinyl alcohol stamp polymer (Example 2), 2 g of polyvinyl alcohol (Celvol 103 from Celanese), 0.5 g of alginic acid sodium salt and 0.15 g of sodium bicarbonate are dissolved in 50 ml of water at 70 ° C. and after cooling to room temperature 250 ml of a 0.1 molar calcium chloride solution are added dropwise in large drops from a syringe without a cannula with slow stirring, spherical particles about 3 mm in size being formed. The particles are isolated by careful filtration through a glass frit and added to a 40 ° C solution of 5 g formaldehyde (37% in water), 50 g concentrated sulfuric acid and 25 g sodium sulfate. After one hour, the solidified spherical particles are isolated by filtration and washed neutral with water. Yield: 43 g of hydrogel as spherical particles.
Beispiel 6: Herstellung eines Hydrogels enthaltend einen linearen Polyvinylalkohol (Vergleichsbeispiel)Example 6: Preparation of a hydrogel containing a linear polyvinyl alcohol (comparative example)
4 g Polyvinylalkohol (Celvol 103 der Fa. Celanese), 0.5 g Alginsäure-Natriumsalz und 0.15 g Natriumhydrogencarbonat werden bei 70°C in 50 ml Wasser gelöst und nach Abkühlen auf Raumtemperatur zu 250 ml einer 0.1 molaren Caiciumchlorid-Lösung in großen Tropfen aus einer Spritze ohne Kanüle unter langsamem Rühren zugetropft, wobei sich ca. 3 mm große sphärische Partikel bilden. Die Partikel werden. durch vorsichtige Filtration über eine Glasfritte isoliert und zu einer 40°C warmen Lösung von 5 g Formaldehyd (37 %ig in Wasser), 50 g konzentrierter Schwefelsäure und 25 g Natriumsulfat gegeben. Nach einer Stunde werden die verfestigten sphärischen Partikel durch Filtration isoliert und mit Wasser neutral gewaschen. Ausbeute: 37 g Hydrogel als sphärische Partikel.4 g of polyvinyl alcohol (Celvol 103 from Celanese), 0.5 g of alginic acid sodium salt and 0.15 g of sodium hydrogen carbonate are dissolved in 50 ml of water at 70 ° C. and after cooling to room temperature to 250 ml of a 0.1 molar calcium chloride solution in large drops from a Syringe added without cannula with slow stirring, whereby spherical particles about 3 mm in size are formed. The particles are. isolated by careful filtration through a glass frit and added to a 40 ° C solution of 5 g formaldehyde (37% in water), 50 g concentrated sulfuric acid and 25 g sodium sulfate. After one hour, the solidified spherical particles are isolated by filtration and washed neutral with water. Yield: 37 g of hydrogel as spherical particles.
Beispiel 7: Untersuchung der Abnutzung des Hydrogels aus Beispiel 5Example 7: Investigation of the wear of the hydrogel from Example 5
In eine 50 ml - Einwegspritze, auf deren Boden sich ein Plastiksieb (Maschenweite 0.75 mm) befindet, wurde 10 g Hydrogel aus Beispiel 5 gegeben. Das Hydrogel wurde mit einem Plastiksieb bedeckt und der Hohlraum über dem Hydrogel mitIn a 50 ml disposable syringe, on the bottom of which there is a plastic sieve (mesh size 0.75 mm), 10 g of hydrogel from Example 5 were added. The hydrogel was covered with a plastic sieve and the cavity above the hydrogel with
Glaswolle befüllt. Die Spritze wurde mit einem Gummistopfen, durch den ein 1 mm - Teflonschlauch führt, verschlossen. Mit Hilfe einer Pumpe wurde durch den Teflonschlauch über einen Zeitraum von einer Woche über das Hydrogel Leitungswasser mit einer Flußrate von 1 ml / min geleitet. Danach wurde das Hydrogel aus der Spritze entfernt und gewogen. Nach einer Woche wurden 9.2 gGlass wool filled. The syringe was closed with a rubber stopper through which a 1 mm Teflon tube runs. With the help of a pump, tap water was passed through the Teflon tube over a period of one week over the hydrogel at a flow rate of 1 ml / min. The hydrogel was then removed from the syringe and weighed. After one week 9.2 g
Hydrogel aus Beispiel 5 isoliert.Hydrogel isolated from Example 5.
Beispiel 8: Untersuchung der Abnutzung des Hydrogels aus Beispiel 6 (Vergleichsbeispiel) In eine 50 ml - Einwegspritze, auf deren Boden sich ein Plastiksieb (MaschenweiteExample 8: Examination of the wear of the hydrogel from example 6 (comparative example) In a 50 ml disposable syringe, on the bottom of which a plastic sieve (mesh size
0.75 mm) befindet, wurde 10 g Hydrogel aus Beispiel 6 gegeben. Das Hydrogel wurde mit einem Plastiksieb bedeckt und der Hohlraum über dem Hydrogel mit Glaswolle befüllt. Die Spritze wurde mit einem Gummistopfen, durch den ein 1 mm - Teflonschlauch führt, verschlossen. Mit Hilfe einer Pumpe wurde durch den Teflonschlauch über einen Zeitraum von einer Woche über das Hydrogel Leitungswasser mit einer Flußrate von 1 ml / min geleitet. Danach wurde das Hydrogel aus der Spritze entfernt und gewogen. Nach einer Woche wurden 8.1 g Hydrogel aus Beispiel 6 isoliert. 0.75 mm), 10 g of hydrogel from Example 6 were added. The hydrogel was covered with a plastic sieve and the cavity above the hydrogel was filled with glass wool. The syringe was closed with a rubber stopper through which a 1 mm Teflon tube runs. With the help of a pump Teflon tubing passed over the hydrogel tap water over a period of one week at a flow rate of 1 ml / min. The hydrogel was then removed from the syringe and weighed. After one week, 8.1 g of hydrogel from Example 6 were isolated.

Claims

Patentansprüche claims
1. Hydrogele enthaltend mindestens ein Polyvinylalkohol-Stempolymer.1. hydrogels containing at least one polyvinyl alcohol stamp polymer.
2. Hydrogel gemäß Anspruch 1 , dadurch gekennzeichnet, daß das Hydrogel neben dem Polyvinylalkohol-Stempolymer weiterer Polyvinylalkohol- Stempolymere enthält.2. Hydrogel according to claim 1, characterized in that the hydrogel contains in addition to the polyvinyl alcohol stamping polymer further polyvinyl alcohol stamping polymers.
3. Hydrogel gemäß Anspruch 1 , dadurch gekennzeichnet, daß das Hydrogel neben dem Polyvinylalkohol-Stempolymer weiterer Polymere ausgewählt aus der Gruppe der Polyvinylalkohole, Polyacrylsäuren, Polymethacrylsäuren, Polyacrylaten, Polymethacrylaten und Polyvinylpyrrolidon enthält.3. Hydrogel according to claim 1, characterized in that the hydrogel contains in addition to the polyvinyl alcohol stamp polymer further polymers selected from the group of polyvinyl alcohols, polyacrylic acids, polymethacrylic acids, polyacrylates, polymethacrylates and polyvinylpyrrolidone.
Hydrogel gemäß Anspruch 1 , dadurch gekennzeichnet, daß das Polyvinylalkohol-Stempolymer mindestens eine Verbindung der Formel l, II und IIIHydrogel according to Claim 1, characterized in that the polyvinyl alcohol stamping polymer comprises at least one compound of the formula I, II and III
Formel I Formel II Formel Formula I Formula II Formula
worin Pol für ein Polymer auf der Basis eines Polyvinylalkohols steht, besonders bevorzugt für ein Homo- oder Copolymer auf der Basis von Polyvinylalkohol, . ganz besonders bevorzugt Polyvinylalkohol, Polyvinylalkohol-Polyvinylacetat- Copolymer, Polyvinylalkohol-Polyethylen-Copolymer, Polyvinylalkohol- Polyvinylchlorid-Copolymer und Polyvinylalkohol-Polyacrylsäuremethylester- Copolymer, und ein Zentralatom bedeutet und ein Atom der 13. bis 16. Gruppe des Periodensystems der Elemente, bevorzugt Kohlenstoff, Silicium, Stickstoff, Phosphor, Sauerstoff oder Schwefel, besonders bevorzugt Kohlenstoff oder Silicium, ist, undwherein Pol represents a polymer based on a polyvinyl alcohol, more preferably a homo- or copolymer based on polyvinyl alcohol. very particularly preferably polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymer, polyvinyl alcohol-polyethylene copolymer, polyvinyl alcohol-polyvinyl chloride copolymer and polyvinyl alcohol-polyacrylic acid methyl ester copolymer, and denotes a central atom and an atom from the 13th to 16th group of the Periodic Table of the Elements, preferably carbon , Silicon, nitrogen, phosphorus, oxygen or sulfur, particularly preferably carbon or silicon, and
X1 jeweils gleich oder verschieden ist, und ein Halogenatom, bevorzugt Fluor, Chlor, Brom oder lod, besonders bevorzugt Chlor, Brom oder lod ist, undX 1 is in each case the same or different, and is a halogen atom, preferably fluorine, chlorine, bromine or iodine, particularly preferably chlorine, bromine or iodine, and
R1 gleich oder verschieden ist, und gleich Wasserstoff oder eine Ci - C2o- kohlenstoffhaltige Gruppe ist, und R2 gleich oder verschieden ist und eine verbrückende Ci - C2o -kohlenstoffhaltige Gruppe zwischen dem Zentralatom Z und der initiierenden Einheit [R3-X1] oder Silicium oder Sauerstoff bedeutet, undR 1 is the same or different and is hydrogen or a Ci - C 2 o-carbon-containing group, and R 2 is the same or different and is a bridging Ci - C 2 o carbon-containing group between the central atom Z and the initiating unit [R 3 -X 1 ] or silicon or oxygen, and
R3 gleich oder verschieden ist und Kohlenstoff oder Silicium bedeutet, und R4 gleich oder verschieden ist und ein Wasserstoffatom oder eine Ci - C20 - kohlenstoffhaltige Gruppe ist, undR 3 is identical or different and represents carbon or silicon, and R 4 is identical or different and is a hydrogen atom or a Ci - C 20 carbon-containing group, and
R5 gleich oder verschieden ist und Wasserstoff oder eine Ci - C2o - kohlenstoffhaltige Gruppe bedeutet,R 5 is the same or different and is hydrogen or a Ci - C 2 o - carbon-containing group,
I eine ganze natürliche Zahl ist und für Null, 1 , 2 oder 3 steht, und m jeweils gleich oder verschieden ist und eine ganze natürlich Zahl ist und für Null, 1 , 2, 3, 4 und 5 steht, und n jeweils gleich oder verschieden ist und eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, und o jeweils gleich oder verschieden ist und 1 oder 2 ist, und p jeweils gleich oder verschieden ist und eine ganze natürliche Zahl ist und für 1 , 2, 3, 4 und 5 steht, und q eine ganze natürliche Zahl ist und für 2, 3 und 4 steht, undI is a whole natural number and stands for zero, 1, 2 or 3, and m is in each case identical or different and is a whole natural number and stands for zero, 1, 2, 3, 4 and 5, and n each is equal to or is different and is an integer and for zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 and 20 is and o is the same or different and is 1 or 2, and p is the same or different and is an integer and is 1, 2, 3, 4 and 5, and q is an integer and stands for 2, 3 and 4, and
Ar ein aromatisches Grundgerüst mit mindestens vier Kohlenstoffatomen ist, bei dem ein oder mehrere C-Atome durch Bor, Stickstoff oder Phosphor ausgetauscht sein können, und wobei bevorzugte aromatische oder heteroaromatische Grundgerüste sich von Benzol, Biphenyl, Naphthalin, Anthracen, Phenanthren, Triphenylen, Chinolin, Pyridin, Bipyridin, Pyridazin, Pyrimidin, Pyrazin, Triazin, Benzopyrrol, Benzotriazol, Benzopyridin, Benzopyrazidin, Benzopyrimidin, Benzopyrazin, Benzotriazin, Indolizin, Chinolizin, Carbazol, Acridin, Phenazin, Benzochinolin, Phenoxazin, die gegebenenfalls auch substituiert sein können, ableiten, und y eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, und z eine ganze natürliche Zahl ist und für 2, 3, 4, 5, 6, 7, 8, 9 und 10 steht.Ar is an aromatic backbone with at least four carbon atoms, in which one or more carbon atoms can be replaced by boron, nitrogen or phosphorus, and preferred aromatic or heteroaromatic backbones are derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, quinoline , Pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, benzopyrrole, benzotriazole, benzopyridine, benzopyrazidine, benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, which may also be substituted, which may also be substituted and y is an integer and is zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 and z is an integer and is 2, 3, 4, 5, 6, 7, 8, 9 and 10.
Ap ein cyclisches nicht-aromatisches Grundgerüst mit mindestens drei Kohlenstoffatomen ist, welches auch Heteroatome wie Stickstoff, Bor, Phosphor, Sauerstoff oder Schwefel enthalten kann, ist, wobei sich bevorzugte aliphatische Grundgerüste aus der Gruppe Cycloalkyl, wie beispielsweise Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, oder aus der Gruppe Cycloheteroalkyl, wie beispielsweise Aziridin, Azetidin, Pyrrolidin, Piperidin, Azepan, Azocan, 1 ,3,5-Triazinan, 1 ,3,5- Trioxan, Oxetan, Furan, Dihydrofuran, Tetrahydrofuran, Pyran, Dihydropyran, Tetrahydropyran, Oxepan, Oxocan, oder aus der Gruppe der Saccharide, wie beispielsweise alpha-Glucose, beta-Glucose, ableiten lassen, und eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, und b eine ganze natürliche Zahl ist und für 2, 3, 4, 5, 6, 7, 8, 9 und 10 steht, und c eine ganze natürliche Zahl ist und für Null, 1 , 2, 3, Ap is a cyclic non-aromatic backbone with at least three carbon atoms, which can also contain heteroatoms such as nitrogen, boron, phosphorus, oxygen or sulfur, preferred aliphatic backbones from the group cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, Cyclooctyl, Cyclononyl, or from the group cycloheteroalkyl, such as, for example, aziridine, azetidine, pyrrolidine, piperidine, azepane, azocane, 1, 3,5-triazinane, 1, 3,5-trioxane, oxetane, furan, dihydrofuran, tetrahydrofuran , Pyran, dihydropyran, Tetrahydropyran, oxepan, oxocan, or from the group of saccharides, such as, for example, alpha-glucose, beta-glucose, and is an integer and is zero, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, and b is an integer and is 2, 3, 4, 5, 6, 7, 8, 9 and 10, and c is an integer and is zero, 1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19 und 20 steht, gleich oder verschieden sein kann, und Null oder Eins ist, ist.4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 and 20, may be the same or different, and is zero or one.
5. Hydrogel gemäß Anspruch 1 , dadurch gekennzeichnet, daß das Polyvinylalkohol-Stempolymer ein Polyvinylalkohol-Copolymer auf der Basis von Polyvinylester-Copolymeren die durch ein Verfahren umfassend die Schritte: A) Radikalische Lösungs- oder Massen-Polymerisation von Vinylestem in Gegenwart eines Radikalbildners und gegebenenfalls in Gegenwart eines Radikalfängers, B) Zugabe einer zur Vernetzung befähigten Polyalkenyl-Verbindung, C) gegebenenfalls Aufarbeitung und Isolierung der gebildeten Polyvinylester- Copolymere, D) Verseifung der in B) hergestellten Polyvinylester/Polyvinylester-polyalken- Mischung oder der unter C) isolierten Polyvinylester-polyalken- Copolymere mit Base unter Ausbildung der PolyvinylalkohoiyPolyvinylalkohol-polyalken-Mischungen bzw. Polyvinylalkphol-polyalken-Copolymeren und Isolierung der Produkte,5. Hydrogel according to claim 1, characterized in that the polyvinyl alcohol stamp polymer is a polyvinyl alcohol copolymer based on polyvinyl ester copolymers by a process comprising the steps of: A) radical solution or bulk polymerization of vinyl esters in the presence of a radical generator and optionally in the presence of a radical scavenger, B) adding a polyalkenyl compound capable of crosslinking, C) optionally working up and isolating the polyvinyl ester copolymers formed, D) saponifying the polyvinyl ester / polyvinyl ester-polyalkene mixture prepared in B) or the mixture isolated under C) Polyvinyl ester-polyalkene copolymers with base to form the polyvinyl alcohol-polyvinyl alcohol-polyalkene mixtures or polyvinylalkolene-polyalkene copolymers and isolation of the products,
dadurch gekennzeichnet, daß es sich bei den in Schritt B) eingesetzten Polyalkenyl- Verbindungen um Verbindungen gemäß Formel IV:characterized in that the polyalkenyl compounds used in step B) are compounds of the formula IV:
Formel IV worin: Formula IV in which:
R6 eine Cβ - C2o -Arylgruppe, eine C5 - C2o-Heteroarylgruppe, eine C4-C2o- Cycloalkylgruppe, eine C4-C o-Heterocycloalkylgruppe oder eine Ci - C o- Alkylgruppe bedeutet, bei der ein oder mehrere nicht direkt benachbarte C- Atome durch ein Element der 5. oder 6. Gruppe der Elemente, bevorzugt Stickstoff, Phosphor, Sauerstoff oder Schwefel, besonders bevorzugt Stickstoff oder Sauerstoff, ersetzt sein können, und R7 gleich oder verschieden ist, und gleich Wasserstoff, Sauerstoff, Schwefel oder eine Hydroxygruppe, eine Carbamoylgruppe, eine Aminogruppe, eine Carboxygruppe, eine Ci - C2o -Alkylcarbonylgruppe, eine Ci - C20 - Alkyloxygruppe, eine C6 - C2o -Aryloxygruppe, eine Iminogruppe, eine Ci - C2o -Alkyliminogruppe, eine C6 - C20 -Alkyliminogruppe, eine Cyanogruppe, eine Ci - C2o- Alkylgruppe, eine Cβ - C2o -Arylgruppe, eine C5 - C20- Heteroarylgruppe, eine C -C2rj-Cycloalkylgruppe, eine C -C2o-Heterocycloalkyl eine C - C2o-Alkylarylgruppe, eine C7 - C30-Arylalkylgruppe, eine C2 - C2o - Alkenylgruppe, eine C2 - C20 - α-Oxy-alkenyl, eine halogenhaltige Ci - C2o - Alkylgruppe, eine C - C20 -Arylgruppe, eine C - C2o-Alkylarylgruppe, eine C - C30 -Arylalkylgruppe oder eine C2 - C2o -Alkenylgruppe bedeutet, undR 6 is a Cβ - C 2 o aryl group, a C 5 - C2o heteroaryl group, a C 4 -C 2 o cycloalkyl group, a C 4 -C o heterocycloalkyl group or a Ci - C o- Alkyl group means in which one or more not directly adjacent C atoms can be replaced by an element of the 5th or 6th group of elements, preferably nitrogen, phosphorus, oxygen or sulfur, particularly preferably nitrogen or oxygen, and R 7 is the same or is different, and is hydrogen, oxygen, sulfur or a hydroxy group, a carbamoyl group, an amino group, a carboxy group, a Ci - C 2 o -alkylcarbonyl group, a Ci - C 20 -alkyloxy group, a C 6 - C 2 o -aryloxy group , an imino group, a Ci - C 2 o alkylimino group, a C 6 - C 20 alkylimino group, a cyano group, a Ci - C 2 o alkyl group, a Cβ - C 2 o aryl group, a C 5 - C 20 - Heteroaryl group, a C -C 2 rj-cycloalkyl group, a C -C 2 o-heterocycloalkyl a C - C 2 o-alkylaryl group, a C 7 - C 30 arylalkyl group, a C 2 - C 2 o - alkenyl group, a C 2 - C 20 - α-oxy-alkenyl, a halogen-containing Ci - C 2 o - alkyl group, a C - C 20 arylg group, a C - C 2 o -arylaryl group, a C - C 30 -arylalkyl group or a C 2 - C 2 o -alkenyl group, and
R8, R9, R10 gleich oder verschieden sind, und gleich Wasserstoff oder eine Ci - C2o - kohlenstoffhaltige Gruppe ist, und e eine ganze natürliche Zahl von 0 bis 40 bedeutet, handelt, erhältlich sind, eingesetzt werden.R 8 , R 9 , R 10 are the same or different, and are hydrogen or a Ci - C 2 o - carbon-containing group, and e is an integer from 0 to 40, is available.
6. Verwendung der Hydrogele gemäß einem der Ansprüche 1 bis 5 im biomedizinischen und pharmazeutischen Bereich, insbesondere zur Herstellung von künstlichem Gewebe oder zur Wundbehandlung, zur Herstellung von Kontaktlinsen, als Trägermaterial zur kontrollierten Freisetzung von Wirkstoffen, als Trägermaterial für Einschluß - immobilisierte Biokatalysatoren, insbesondere in der Abwasserbehandlung, als Trägermaterial für Übergangsmetallkatalysatoren, als Material für die Herstellung von Reaktivmembranen, als Zusatz zu Bohrflüssigkeiten, insbesondere in Bohrspülungen, als Verdrängungsmittel bei der Ölförderung, als Additiv in Baustoffen, insbesondere Dispersionen und Emulsionen, als Zusatzmittel zu hochviskosen Flüssigkeiten, insbesondere zur Verbesserung des Fließverhaltens und zum schnelleren Transport, und als Bestandteil von Kosmetikartikeln. 6. Use of the hydrogels according to one of claims 1 to 5 in the biomedical and pharmaceutical field, in particular for the production of artificial tissue or for wound treatment, for the production of contact lenses, as a carrier material for the controlled release of active substances, as a carrier material for inclusion - immobilized biocatalysts, in particular in wastewater treatment, as a carrier material for transition metal catalysts, as a material for the production of reactive membranes, as an additive to drilling fluids, especially in drilling fluids, as a displacement agent in oil production, as an additive in building materials, especially dispersions and emulsions, as an additive to highly viscous liquids, especially for Improvement of flow behavior and for faster transport, and as part of cosmetic articles.
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